Computational studies on the Rh-catalyzed carboxylation of a C(sp2)–H bond using CO2

2017 ◽  
Vol 7 (16) ◽  
pp. 3539-3545 ◽  
Author(s):  
Xiangying Lv ◽  
Linhui Zhang ◽  
Beibei Sun ◽  
Zhi Li ◽  
Yan-Bo Wu ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Computational Studies ◽  
Agostic Interaction

CO2 insertion is facilitated by the critical effects of a Lewis acid and an agostic interaction.

Computational Studies on the BF3-Catalyzed Cycloaddition of Furan with Methyl Vinyl Ketone:  A New Look at Lewis Acid Catalysis

2000 ◽  
Vol 65 (20) ◽  
pp. 6613-6619 ◽  
Author(s):  
Martín Avalos ◽  
Reyes Babiano ◽  
José L. Bravo ◽  
Pedro Cintas ◽  
José L. Jiménez ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Acid Catalysis ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Computational Studies ◽  
Lewis Acid Catalysis ◽  
Methyl Vinyl ◽  
New Look

scholarly journals Coordination Behavior of [Cp″2Zr(µ1:1-As4)] towards Lewis Acids

Molecules ◽  
2021 ◽  
Vol 26 (10) ◽  
pp. 2966
Author(s):  
Veronika Heinl ◽  
Gábor Balázs ◽  
Sarah Koschabek ◽  
Maria Eckhardt ◽  
Martin Piesch ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Lewis Acid ◽  
Reaction Temperature ◽  
Lewis Acids ◽  
Computational Studies ◽  
Coordination Modes ◽  
Coordination Numbers ◽  
Coordination Behavior

The functionalization of the arsenic transfer reagent [Cp″2Zr(η1:1-As4)] (1) focuses on modifying its properties and enabling a broader scope of reactivity. The coordination behavior of 1 towards different Lewis-acidic transition metal complexes and main group compounds is investigated by experimental and computational studies. Depending on the steric requirements of the Lewis acids and the reaction temperature, a variety of new complexes with different coordination modes and coordination numbers could be synthesized. Depending on the Lewis acid (LA) used, a mono-substitution in [Cp″2Zr(µ,η1:1:1:1-As4)(LA)] (LA = Fe(CO)4 (4); B(C6F5)3 (7)) and [Cp″2Zr(µ,η3:1:1-As4)(Fe(CO)3)] (5) or a di-substitution [Cp″2Zr(µ3,η1:1:1:1-As4)(LA)2] (LA = W(CO)5 (2); CpMn(CO)2 (3); AlR3 (6, R = Me, Et, iBu)) are monitored. In contrast to other coordination products, 5 shows an η3 coordination in which the butterfly As4 ligand is rearranged to a cyclo-As4 ligand. The reported complexes are rationalized in terms of inverse coordination.

Lewis Acid Coordination Redirects S-Nitrosothiol Reduction

2020 ◽  
Author(s):  
Valiallah Hosseininasab ◽  
Alison C. McQuilken ◽  
Abolghasem (Gus) Bakhoda ◽  
Jeffery A. Bertke ◽  
Qadir K. Timerghazin ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Lewis Acids ◽  
Reduction Potential ◽  
Chemical Reduction ◽  
Physiological Responses ◽  
Outer Sphere ◽  
Intramolecular Electron Transfer ◽  
Computational Studies ◽  
Reduction Potentials ◽  
Initial Reduction

<i>S</i>-Nitrosothiols (RSNOs) serve as air-stable reservoirs for nitric oxide in biology and are responsible for a myriad of physiological responses. While copper enzymes promote NO release from RSNOs by serving as Lewis acids capable of intramolecular electron-transfer, redox innocent Lewis acids separate these two functions to reveal the effect of coordination on structure and reactivity. The synthetic Lewis acid B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> coordinates to the RSNO oxygen atom in adducts RSNO-B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>, leading to profound changes in the RSNO electronic structure and reactivity. Although RSNOs possess relatively negative reduction potentials (-1.0 to -1.1 vs. NHE), B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> coordination increases their reduction potential by over 1 V into the physiologically accessible +0.1 V vs. NHE. Outer-sphere chemical reduction results in formation of the Lewis acid stabilized hyponitrite dianion <i>trans</i>-[LA–O–N=N–O–LA]<sup>2–</sup> (LA = B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>) that releases N<sub>2</sub>O upon acidification. Mechanistic and computational studies support initial reduction to the [RSNO-B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>]<sup>•/- </sup>radical-anion susceptible to N-N coupling prior to loss of RSSR.

ChemInform Abstract: Computational Studies on the BF3-Catalyzed Cycloaddition of Furan with Methyl Vinyl Ketone: A New Look at Lewis Acid Catalysis.

ChemInform ◽  
2001 ◽  
Vol 32 (4) ◽  
pp. no-no
Author(s):  
Martin Avalos ◽  
Reyes Babiano ◽  
Jose L. Bravo ◽  
Pedro Cintas ◽  
Jose L. Jimenez ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Acid Catalysis ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Computational Studies ◽  
Lewis Acid Catalysis ◽  
Methyl Vinyl ◽  
New Look

Cyanide and Azide Anion Complexation by a Bidentate Stibonium-Borane Lewis Acid

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1199-1205 ◽  
Author(s):  
Casey R. Wade ◽  
François P. Gabbaï
Keyword(s):  
Lewis Acid ◽  
Lewis Acids ◽  
Natural Bond Orbital ◽  
Orbital Method ◽  
Computational Studies ◽  
Cyanide Complex ◽  
Acid Anion ◽  
Anion Complexation ◽  
Azide Ligand ◽  
Complex Features

Abstract Our ongoing interest in the chemistry of polyfunctional Lewis acids has led us to investigate the reaction of the stibonium-borane [o-(Ph2MeSb)(Mes2B)C6H4]+ (1+) with cyanide and azide, two toxic anions. Both anions react with 1+ to afford the corresponding neutral complexes 1-CN and 1-N3. Structural and computational studies show that the coordinated anion interacts with both the boron and antimony atoms of the bidentate Lewis acid. While the azide complex features a typical κ2N1 : N1 bridging azide ligand, the cyanide complex possesses a cyanoborate moiety whose cyanide interacts side-on with the stibonium center. The Lewis acid-anion interactions observed in these complexes have also been studied computationally using the Natural Bond Orbital method

Lewis Acid Coordination Redirects S-Nitrosothiol Reduction

2020 ◽  
Author(s):  
Valiallah Hosseininasab ◽  
Alison C. McQuilken ◽  
Abolghasem (Gus) Bakhoda ◽  
Jeffery A. Bertke ◽  
Qadir K. Timerghazin ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Lewis Acids ◽  
Reduction Potential ◽  
Chemical Reduction ◽  
Physiological Responses ◽  
Outer Sphere ◽  
Intramolecular Electron Transfer ◽  
Computational Studies ◽  
Reduction Potentials ◽  
Initial Reduction

<i>S</i>-Nitrosothiols (RSNOs) serve as air-stable reservoirs for nitric oxide in biology and are responsible for a myriad of physiological responses. While copper enzymes promote NO release from RSNOs by serving as Lewis acids capable of intramolecular electron-transfer, redox innocent Lewis acids separate these two functions to reveal the effect of coordination on structure and reactivity. The synthetic Lewis acid B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> coordinates to the RSNO oxygen atom in adducts RSNO-B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>, leading to profound changes in the RSNO electronic structure and reactivity. Although RSNOs possess relatively negative reduction potentials (-1.0 to -1.1 vs. NHE), B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> coordination increases their reduction potential by over 1 V into the physiologically accessible +0.1 V vs. NHE. Outer-sphere chemical reduction results in formation of the Lewis acid stabilized hyponitrite dianion <i>trans</i>-[LA–O–N=N–O–LA]<sup>2–</sup> (LA = B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>) that releases N<sub>2</sub>O upon acidification. Mechanistic and computational studies support initial reduction to the [RSNO-B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>]<sup>•/- </sup>radical-anion susceptible to N-N coupling prior to loss of RSSR.

Competition between Hydrogen Bonds and Lewis Acid-Base Interactions in the Equilibria between Bis(pentafluorophenyl)borinic Acid and Pyridine: Insights from NMR, Diffractometric and Computational Studies

2013 ◽  
Vol 227 (6-7) ◽  
pp. 751-773 ◽  
Author(s):  
Daniela Maggioni ◽  
Tiziana Beringhelli ◽  
Guiseppe D' Alfonso ◽  
Maria Carlotta Malatesta ◽  
Pierluigi Mercandelli ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Lewis Acid ◽  
Computational Studies ◽  
Acid Base ◽  
Borinic Acid

scholarly journals Enhancement of the physicochemical properties of [Pt(dien)(nucleobase)]2+ for HIVNCp7 targeting

2017 ◽  
Vol 8 (2) ◽  
pp. 1269-1281 ◽  
Author(s):  
S. D. Tsotsoros ◽  
P. B. Lutz ◽  
A. G. Daniel ◽  
E. J. Peterson ◽  
R. E. F. de Paiva ◽  
...  
Keyword(s):  
Physicochemical Properties ◽  
Lewis Acid ◽  
Computational Studies ◽  
Stacking Interactions ◽  
Rna Interaction

Building from tryptophan to the tryptophan-containing HIV Nucleocapsid 7 (HIVNCp7) protein we combine biophysical and computational studies to enhance stacking interactions of purines through platination. The incorporation into a weak Lewis acid electrophile, [Pt(dien)(Nucleobase)]2+ may lead to disruption of the HIVNCp7-RNA interaction.

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